Heat-producing compositions

ABSTRACT

This invention pertains to heat-producing compositions which are non-toxic and useful in cleaning pipes, drains, and the like. These compositions are comprised of powdered aluminum, an alkali metal nitrate and an alkali metal salt of an acid having at least one hydrogen atom with an ionization constant in water not exceeding 6.0 X 10 9.

United States Patent 1 91 1111 3,875,083

Murtaugh 1 1 Apr. 1, 1975 HEAT-PRODUCING COMPOSITIONS 5.503.890 3/1970 Davisson et al 252/157 x 3, 4 N 364 X 1 1 Inventor: Justin Mumugh, Guflfmd. 3.218.332, 1211331 HEFTTfFET'. .5251 [73] Assignee: The Drackett Company, Cincinnati. OTHER PUBLICATIONS Ohio Mahan, University Chemistry. Addison-Wes1ey Pub- 1 Filedi J 1973 lishing Co., 1nc., New York, 1965, pp. 183 and 193 to 195 21 A l. N 373.955 i 1 pp 0 Bubor, Bas1c College Chemistry. 2nd Ed., Thomas Y.

Related Applwatwn Data Crowell (70., N.Y.. 1953. pp. 255-258. [63] Continuation-impart of Scr. No. 72,752, Sept. 16.

1970- llbflndoncd Primary E.\'aminerLeland A. Sebastian Auurney. Agent. or Firn1D21vid J. Mugford; George [52] US. Cl 252/535, 252/135, 252/157, ,1\ M ti 252/188.3, 252/527 {5 l] llll. 7/48 57 158] Field of Search 252/99. 102, 157, 188.3 R, l Thls 1nvent1on pertams to heat-producmg composi- 252/527, 535

t1ons whlch are non-tox1c and useful In cleamng p1pes. 1-561 3:122:o1"51221212121352:2113112511:11:; UNITED STATES PATENTS and an alkali metal salt of an acid having at least one hydrogen atom with an ionization constant in water 2\ I011 r t i 1 1 r v. '9 3.344.075 9/1967 Graham ct a1 252/157 not exceedmg X 10 3.471.407 10/1969 Spring 252/157 38 Claims, 3 Drawing Figures f 50 Sample A- a a B: 000 E 50 TIME (mm) 11 lZ3455789101112131415151781920 Z5 TIMECmin.)

1'' THNEEAFR H875 SilEU 1 UP 3 8 7 .u was:

Sample A= mmmzu B=ooo c:

w m w m w. 2 N N W m. A Tu S 0, U .Y 8

12 a4 5 a 1 a 91011121314151617181920 TIME (mm) 3 911 R IEEITED 11375 3.875.083

TEMPERATURE C a a a Sample E- F x-x-x I G 0-H TIME (mm) INVE TOR JUSTIN J.M UFTAU H AEI'TORNEY TEMPERATURE C "QT EZl- L; $5"; .675 3.875.083

K SITY Sample E 0-0-0 50 l C- xx--x TIE (min) INVENT ATTORNEY HEAT-PRODUCING COMPOSTTIONS This application is a continuation-in-part of application Ser. No. 72.752. filed Sept. 16. 1970. now abandoned.

This invention is concerned with new and improved compositions which are heat-producing upon contact with water and which are useful as drain cleaners and the like.

Dry compositions which liberate heat upon contact with moisture are well-known and this type of composition has also been used in the drain cleaning art. For ex ample. U.S. Pat. No. 2.773.040 (Walton) discloses heat-liberating compositions containing aluminum and an alkali metal hydroxide. US. Pat. No. 2.816.0l 2 (Walton) discloses heat-producing compositions containing aluminum, an alkali-metal hydroxide, a watersoluble inorganic: nitrate. and copper.

The compositions of the present invention represent an improvement over these prior art compositions and are comprised of powdered aluminum, an alkali metal nitrate, and a salt of an organic or inorganic acid. such as tri-sodium phosphate. or tri-potassium phosphate.

The novel drain cleaning compositions of the invention are nontoxic and have eliminated the use ofcaustic. It has been found that powdered aluminum will react with alkali metal salts of acids having at least one hydrogen atom with an ionization constant in water not exceeding 6.0 X l" to produce excellent heatproducing drain cleaners.

In accordance with the present invention. the new drain cleaning compositions are comprised of( l powdered aluminum having a particle size of from about I to 300 microns, in an amount ranging from about 0.5 to about l6.7'/( by weight; (2) an alkali metal nitrate. in an amount ranging from about l6.0 to about 59.0% by weight: and (3) an alkali metal salt of an acid having at least one hydrogen atom with an ionization constant in water not exceeding 6.0 X in an amount ranging from about 36.0 to about 73.2% by weight.

Generally. the flow of water through a drain becomes obstructed by the accumulation of organic material lodged in the U-bend of the drain trap. The organic materials are usually bound together by a hot melted material. such as a fat. oil. or grease, which has cooled and solidified. For example. binding materials commonly found in a household drain are beef tallow. human fat deposits. and furniture wax residues. In order to unclog a drain. a good drain cleaner should be capable of producing a sufficient amount of heat to re-melt this binding material and dissolve the clog in order that the organic materials forming the clog may be carried in the flow of water through the drain.

ln accordance with the invention. it has been deter mined that when about 0.5 to about l6.7'/1 by weight of a powdered aluminum. about 16.0 to about 59.0% by weight of an alkali metal nitrate, and about 36.0 to about 73.27: by weight of an alkali metal salt of an acid having at least one hydrogen atom with an ionization constant in water not exceeding 6.0 X 10 are combined. an effective non-toxic, heat-producing drain cleaner is produced which is capable of generating a sufficient amount of heat to raise the temperature of water above the minimum temperature necessary to remelt the clogging material in the drain in order to dissolve the clog. The relative amounts of these materials may be varied depending on how much heat is desired to be generated or the time desired for the composition to unclog the drain. However. the drain-cleaning composition should be capable of generating heat sufficient to raise the temperature of water in the drain at the point of the clog above the minimum temperature necessary for dissolving the clog.

The following acids are contemplated by the present invention:

Compound Ionization ('onstant Salicylic Acid Lt) X Ill- Alpha Amino-acetic Acid L67 X l0 Hydroquinone 4.5 X lll" Para Hydroxybenzoic Acid 4.8 X 10"" Saeeharin 2.l X l(l-"- Carbonic Acid 56] X ltl"" Pyrophosphoric Acid 6 X lll' Ethylenediantinctetraaeetie Acid 5.5 X 10 Diethylenetriaminepentaacetie Acid 3.8 X l0' N-Hydroxyethylenediaminetriaeetic Acid L86 X llY'" Nitrilotriacctic Acid L86 X llY Phosphoric Acid 4.8 X Ill The salts of these acids used in the drain-cleaning compositions of the present invention are preferably the alkali metal salts such as sodium. potassium. lithium. rubidium. and cesium.

When a salt of an acid which has at least one hydrogen with an ionization constant of 6.0 X l0" or less reacts with aluminum powder. frce hydrogen is liberated. In the formulation of caustic heat-producing drain cleaners. the addition of oxidizing agents and particularly water-soluble nitrates have long been used to oxidize free hydrogen to non-gaseous compounds. la the oxidation-reduction reaction between free hydrogen and the nitrate ion. molecular hydrogen with zero valence is oxidized to combined hydrogen with a valence of plus one. The nitrogen combined in the nitrate ion with a valence of plus five is reduced to ammonia where it has a valence of minus three or to nitrate with a valence of plus three. The benefits are two-fold. The liberation of free hydrogen is prevented and the reaction is exothermic and thereby adding substantially to the generation of heat. Alkali metal nitrates are prel'errcd.

The third hydrogen of phosphoric acid has an ionization constant in water of 4.8 X 10". When properly formulated in accordance with the invention. the trisodium salt of this acid. which is used widely in industry and the household and not considered toxic or especially hazardous. can be used to make a good heatproducing drain cleaner. When a salt such as tri-sodium phosphate is combined with aluminum powder and the surface area is controlled by particle size. the reaction is exothermic and can be regulated so as to pass through a slowly rising temperature-time period until a vigorous turbulent hot reaction mixture is obtained. When these ingredients are combined with a watersoluble nitrate. mixed or eonglomerated by way of tusion. compacted or granulated and pelletized to a limited particle range of 210 to 4760 microns. preferably H4l to 2380 microns. an excellent. non-toxic. nonhazardous drain cleaner is obtained. A balanced equation for the described reaction is given below:

reaction rates it is important that all of the components are substantially homogeneously distributed. By preparing the compositions in accordance with the invention there is a delayed but controllable induction period of the reaction of the components with the water at the site of the drain impediment.

The rate of reaction will depend chiefly on the temperature of the water and the particle size ofthe aluminum. For any given particle size the rate of reaction will increase as the temperature of the water increases. It is important that the initial heat production must be such to provide l heat loss due to dissipation from the system and (2) sufficient heat to raise the temperature of the surrounding water and suspended solids so that the auto-catalytic effect of temperature will provide an increased rate of reaction resulting in a hot boiling mix' ture. An ideal formulation would contain aluminum particles of different sizes. This would provide for initial heat generating by smaller particles and then a slower extended reaction of a selected distribution of somewhat larger particles. Although such a distribution of aluminum particle size is desirable, it is not necessary to a useful product. It has been found that by formulating with mixtures of aluminum powders having a particle size range of from below one micron to 300 microns and preferably from 15 to 50 microns, a very effective heat-producing drain cleaner can be produced.

From the equation given for the reaction of aluminum, tri-sodium phosphate, sodium nitrate and water, one can calculate 2 l 5.76 g. of aluminum will react with 8]).86 g. oftri-sodium phosphate and 255.03 g. of sodium nitrate. This is a ratio of 8 moles of aluminum to moles of tri-sodium phosphate to 3 moles of sodium nitrate. The 8-5-3 ratio given above would contain I679? aluminum powder. A product composition containing this much aluminum would provide more heat than would be desirable for the usual 30-45 g. charge added to a clogged drain. A heat-producing composition, according to the invention, can be prepared with an aluminum powder content as low as 0.5%, however, for best performance with maximum safety it is pre ferred to use a composition containing 4. l'/: aluminum.

The reaction ratio of 8-5-3 requires 3 moles of sodium nitrate or L1 8 g. of sodium nitrate for each gram of aluminum powder. This is the theoretical lower limit which can be formulated without liberating free hydrogen gas. To provide for a greater margin of safety, it is preferred to use 4 to 8 g. ofsodium nitrate or its equivalent as potassium nitrate for each gram of aluminum powder.

From the equation it can be seen that five moles of tri-sodium phosphate, or any other reacting salt, is required for each 8 moles of aluminum powder. In the case of tri-sodium phosphate, this is 3.8 g. for each gram of aluminum powder. Maximum usage for heat generation and insured conversion to the water soluble aluniinate ion is best carried out in the presence of an excess of the reacting salt. Compositions may be prepared with as low as l07( tri-sodium phosphate. This would be a molar ratio of 0.4 moles for each mole of aluminum powder at the preferred aluminum powder composition of 4. l7r. For reasons of simplicity most of the foregoing discussion has been limited to aluminum powder, tri-sodium phosphate and sodium nitrate.

Due to the low water solubility of disodium hydrogen phosphate hydrate (Na HPO l2H O), one of the products of the reaction when the ingredients are mixed in the presence of water, it is preferred to use potassium salts or to incorporate a considerable portion of potassium ions into the formulation. Na HPO, IZH O has a melting point of 351C. and a solubility of only 4.15 g. per 100 ml. in cold water. lfthe products of the reaction mixture in my new drain cleaner are not washed out of the drain while still hot, the Na HPO, l2H O can crystallize out of solution. By using tripotassium phosphate and sodium nitrate or tri-sodium phosphate and potassium nitrate, crystallization of insoluble di-sodium hydrogen phosphate hydrate is prevented even if the reaction products are not flushed from the drain before cooling.

Thus, the presence of potassium ions prevents the crystallization ofinsoluble Na- HPO l2H O which has a solubility of 4.15 grams per I00 ml. of cold water. The formulations of the present invention exceed this value by more than 3007:.

The preferred compositions according to the invention include non-aqueous, tacky liquid surfactants such as sulfonated mineral oil (cg. Twitchells) or the combinations of mono and diphosphate esters of ethoxylated linear alcohol (cg. GAFACS) or oxyethylatcd primary straight chain alcohols wherein the alcohols contain from 12 to 20 carbons and 7r ethylene oxide is used, (e.g. Plurofacs). However, any other tacky material may also be used.

In order to illustrate the invention, the following examples are given EXAMPLE I 59.0 g. of potassium nitrate, 36.0 g. of tri-sodium phosphate and 5.0 g. of aluminum powder were mixed and fused at 360C. The fused mixture was allowed to cool and then granulated. 30.0 g. of granulated material were added to ml. of water at 30C. in a 300 ml. test tube. After 5 minutes the temperature of the water increased to l00C. The temperature rise was accompanied by vigorous agitation in the lower portion of the test tube. The 100C. temperature was maintained for 6 minutes.

EXAMPLE 2 20.0 g. of sodium nitrate were mixed with l8.3 g. of tri-potassium phosphate and L? g. of powdered aluminum. The mixture was heated over a burner until fusion of the sodium nitrate occurred. Upon cooling, a hard cake was formed. The cake was granulated to about 6-20 mesh and 30.0 g. added to I00 ml. of water in a large test tube. A slow temperature rise was observed, starting at 25C. and going up to 50C. in 8 minutes. The temperature then increased rapidly to l03C. and held there for seven minutes.

EXAMPLE 3 3.0 g. of powdered trisodium phosphate, 1.2 g. of aluminum powder, and 0.8 g. of potassium nitrate were fused at 380C. After cooling, the fused mixture was granulated and added to 5.8 g. of potassium chloride, 9.8 g. of potassium nitrate and [0.0 of granular trisodium phosphate. 30.0 g. of this mixture were added to [00 ml. ofwater at 25C. in a 300 ml. test tube. After 2 minutes, the temperature increased to 99C. in the lower half of the test tube.

EXAMPLE 4 1440 g. of tri-potassium phosphate, 60 g. of Plurofax A-38 (a non-ionic surfactant) and 137i g. of sodium nitrate were mixed and powdered by passing through a hammer mill. After grinding, 2400 g. olthe powdered both sides of the trap until it reached the level of the mixture were mixed with 107.5 g. of aluminum powder. exit side runoff. As illustrated in the following examples 250 g. otwhite mineral oil. and .65 g. of green pigment shown in Table l, 100 grams of the ingredients oteom- (Phthalo green). The mix was then pelletized with at positions of this invention, varied in relative proporlaboratory model "California Pellet Mill" using a 3/l6 5 {ions f i di m f h m l were mixed to X 1 inch die. The resulting green p l t were very l lt obtain a homogenous mixture, which was then pressed When a 30 g. sample was added to 100g. of ater a into it) individual til-gram tablets at 24,000 lbs. per 25C. in a 300 ml. test tube, the temperature of the square inch. The lil-gram tablets were then broken water in the lower halt'ofthe test tube increased slowly d d granulated to about 34] m h r 2330 i. over a 5-minute period to lC. At 100C, the pellets in cron size. The test sample weight of the granulated mm disintegrated and a churning action was observed. t m], h n in T ble for ea h example, was then added to the closed drain trap, after which one cup of EXAMPLE water was added to the inlet side, raising the water level in the inlet side higher than in the exit side. A thermom- 91) gof POtassium nitrate were mixed Wlth gof IS cter was placed in the inlet side so that the thermome- T t h ll 82 (11 iquid SulftmiC a yp fillrfilcter bulb was at or near the location of the clog and test tant). After the pota ium nitrate was added t he rsample. in all examples of Table l. a hot solution develfactant L23 g. of aluminum powder were added. Upon oped at the location of the clog. As the hot mixture additional mixing, the aluminum powder adhered t melted the clog. water from the inlet side of the trap the surface ofthe potassium nitrate. 7.5 g. oitri-sodium d th h th d t the exit ide, a hown b th phosphate and l L67 g. of potassium chloride w water flow from the exit side of the drain. After an adthcn added. The formulation was mixed and add d t ditional 5 minutes from the time that the exit side water I00 ml. of water at 25C. in a 300 ml. test tube. The flow began, l liter of water was added to the inlet side, temperature increased slowly; but after l5 minutes the which ran off at the exit side evidencing an uninhibited temperature of the water in the lower portion of the 25 water flow. For all examples given in Table l, the matetest tube had increased to 100C. and the reaction prorial originally used to make the clog washed out of the eeeded with vigorous agitation. trap. At this time, the drain was completely unclogged it can be seen from the above examples that the relaand free flowing. tive proportions of the ingredients may be varied in accordance with this invention, heat-producing greatly.The variation olrclative proportions ofingrcdi-' 3O compositions comprising powdered aluminum, in an cnts allowed in producing an effective heat-generating amount front about 0.5 to about I677: by weight; an drain cleaner composition can be shown by utilizing the alkali metal nitrate. in an amount from about 16 to compositions of this invention in the following drain about 597: by weight; and an alkali metal salt of an acid cleaner test system: wherein the acid has at least one hydrogen atom with Inlet Sire/ Inlet. Side Exit Side Runoff 5 Q Exit Side Runoff R.- Drain Trap A 25 gram mixture, consisting of 2'/( hair, 40% calan ionization constant not exceeding 6.0 X l0", in an eium soap curd, 20% coffee grounds, and 387! hot amount from about 36 to about 73.2% by weight, are melted bceffat, was placed at the bottom oithe U-bend effective drain cleaners. of a drain trap in a common household IA inch metal As shown by the following examples in Table l, comdrain. The clog mixture was constructed so as to compositions prepared, as described above, were effective pletcly obstruct the flow of water from the inlet side to in dissolving a clog in the drain allowing a free How of the outlet side of the drain trap. Water was added to water.

TABLE I Example No. Weight of Sample l'inie Required Temp. at

Added to Clogged to Open Drain (log When Example No. l C4 Drain (g) (min.] Opened (Cl Ingredient Na PO, 36.0 Na N0 mo Aluminum Powder (2) .5 Na(iluconate ltH) NaCl 375 TABLE l-Conlinued Weighl of Sample Added in (logged 'l'ime Required In Open Drain Temp. a! (lug when Example Nu '4 Drain lg.) lmin.) Opened 4(l Example No. 2 Ingredient Nn; P() 36A] Nu NO, lb!) Aluminum l'muler ill lb? Nnfl 31 ,3

HllHl'Z 3O 7 NH Example Nu. lngredienl Nam"), 36.!) Nu N0 59.0 Aluminum Powder (2) 5.0

lUlHl'i fill 8 [0|] Exnmnle Nu, J Ingredient Nu PU. 36." NuN() 50." Aluminum Puwder Ill ,5 NaCl 4 5 Example Nu. S Ingredient Nu PO 73.] Na NO lhll Aluminum Powder (2) .5 Null! l(l.3

HNHVZ 75 9 90 Exumnle Nu. h Ingredient Na i), 7342 Na NO HM) Aluminum Pmuler l l l 10.8

HNHI'F 5H \J Hlll ExnmEle No. 7 Ingredient Nu PO, 36.0 Nu NO 47,3 Aluminum Powder l lfi.7

HNLUQ 50 1: Hill Example No. R Ingredient NauPO, 5011 Na NO;. 495 Aluminum Pmuler (ll ,5

llllHVi 75 3 91] Example 9 Ingredient a a 30.1] K N0 lhll Aluminum Ponder (3) .5 Nn-(jlucnnule lllll KCl 37.5

lillHlTv' 75 l:

Example ll] lngrediem K PO, .lhll K NO I61) Aluminum Pmuler (21 l(v.7 K('l 3L3 Hlllill'i 50 I Ill:

Emmnle ll MPO. .mn K NO, 591) Aluminum l'muler Hi 5 ,(l

HNHI'? 5H 7 m lixumple l2 ln reilienl MPO, in." K NO, sun Aluminum l'muler (3) 5 K (I 4.5

lllllll"; 75 S 93 TA BLE Continued Weight of Sample Added in (logged 'Iime Required In Open Drain ExannpIe Nu. Drain lg.) (min.I Opened Example l3 Ingrediem K PO, 73.1 K NO I(\.I) Aluminum Powder 1 l I .5 K(I IUJ Emmnle I4 Ingredient K PO 73.2 K N0 N11) Aluminum Powder I I I III .8

I000 50 I1 I03 Exum Ie I5 Ingredient K,,P(), 36.0 K NCO; 47.3 Aluminum Pnwder (3) 16.7

Exumnle In Ingredient n l 50.0 K NO 49.5 Aluminum Pnwder I2] .5

worm 7s 7 m Exumnle l7 Ingredient N'.\; PO. 40.0 K NO 20.0 Nu-(ilueonme 3.0 Aluminum Powder (2] 4.2 K (I 32,3

IOILlV/i 30 7 I02 limmgle I8 Ingredient N u cO 3h .0 Nu N0 16.0 Aluminum (3) .5 Nu-Glucnnme III.0 NuCl 37.5

Exiun Ie I) Ingredient Nan- C0 36.0 Nu NO m0 Aluminum Puu'der I3] [6.7 NuCI 3| .3

Exumnle 20 Ingredient Nu- C'O 311.0 NuNO; 50.0 Aluminum Powder (3] 5.0

Exmnnle II Ingredient 010 (1) 311,0 Nu NO; 59.0 Aluminum Pnwder I3] .5 Nu CI 4.5

l00.0')i III II) ExzlmEIe 22 Ingredient N u. 7 3 .2 Nu NO HUI Aluminum Powder I Z) .5 NzlCl I0} I00.Il'rl 75 I6 I00 TABLE IContinued Weight of Sample Time Required Temp. at Added to Clogged to Open Drain Clog When Example No. Drain (g.) (min Opened Examnlc H lngrcdicnt Dicthylcnctrinminupcntuacetic Acid (Punt-u- Sudium Stilt) SlHl KNO 3",!) Aluminum Puwdcr (3] 4,2 K(l [5,8

lOiLllZi 5" 14 I03 Exumnlc 5| Ingredient Succhitrin (Sntlium Sult) 36.0 KNO, um) Aluminum Puwdcl' l3) l(\.7 KCI 31.3

lllIHV/i 5!) ll] H) Exumnlu 52 lugrctliunt Succlmrin (Sndium Salli] 73.2 NuNO lbwll Aluminum Pnwdur I) .5 NaCl Exumnlc 53 ln rcdicnt Szicchnrin (Sodium Salli) 501i KNO 3",!) Aluminum Puwtlcr (I) 4.2 KCl l5 .8

lOllll'Z 5U l7 ll):

Exumnlc 54 ingredient PKITH Hydruxyhcnznic Acid (Di-Sodium Salt) 36.0 KNO; lhtl Aluminum Puwdcr (3) 167 K (I ."ll .7

HNHVZ 5(1 16 '49 Exnmglc S5 Ingredient Puru Hydmxyhcnznic Acid lDi-Sodium Stilt) 73.0 NuNQ, l6." Aluminum Powder l l l .5 NuCl l().3

HNHIW 75 l4 K4 Exzlmnlc S6 Ingredient Para Hydruxyhcnzoic Acid [Di-Sodium Suit) 50.0 KNO 3011 Aluminum Puwdci' (2) 4,2 KCl 151% IOlLUfi 5U l1 H13 Exumnlc 57 Ingredient Hydroquinnnc (Sodium Sultl 36.0 KNO 1611 Aluminum Powder (3) I67 KCl 3 l ,7

Examnlc 58 ingredient Hydmquinonc [Sodium Salt) 710 NaNO 3 I61) Aluminum Powder l l .5 NaiCl l0} limit"; 75 ll 92 TABLE 1- Continued Weight of Sample Time Required Temp. at Added to Clogged to Open Drain Clog When Example N0, Drain (g.J lmin.) Opened (C) ingredient Hydroquinone (Sodium Salt) 50.0 KKK): 30.4] Aluminum Ponder [2) 42 l" lll0.(l'/r .lll K 103 Example ht) Ingredient Alpha Aminuneetie Aeid (Sodium Sallll 36.0 KNO [(1.0 Aluminum Powder (2) |h.7 KCl 31 .7

100.0% 50 J ll Example (sl Alpha Aminoucetie Acid lSodium Salt) 73.0 NaNfL, lhll Aluminum Powder I .5 NaCl I000 75 ll] '4) Example 62 Alpha Aminoaleetic Acid (Sodium Salt) 50.0 KNU1 30.0 Aluminum Powder (2) 4.2 L

llllHl'K 104 Ingredient Salicylic Acid (Di-Sodium Salt) 36.0 KNO: mo Aluminum Powder (3) lfs.7 KC] 3| .7

Example 64 Ingredient Salicylic Acid (Di'Sodiunt Salt) 73.0 NaNO 16,0 Aluminum Powder l l .5 NaCl l().]

[000% Ill )1 Example (15 Ingredient Salicylic Acid (Di-Sodium Salli 50.0 KNO 30.0 Aluminum Powder (2] 42 KCl ISM lll0.ll'% 30 l'l l04 Notes to TAHLF l (l l Alummum Po dur m 197 micron particle size (I l Aluminum Ponder ltl lo 10 nllkffl" particle sin: (1 l Alumlnuni Ponder l in K micron particle sin- Sodium or potassium chloride and sodium gluconate were used in some compositions of the above-listed examples as fillers and as hinders to aid in preventing segregation of ingredients in order to maintain a homogeneous distribution of ingredients in the composition.

As can be seen from the examples in Table l, the heat-producing compositions of this invention are efl'ectivc in dissolving a clog, and subsequently, cleaning a drain in a relatively short period of time. Also, it can be seen from the above examples, that the relative proportions of ingredients in the heat-producing compositions, the weight of sample ot'the composition added to the clogged drain. the time required to open the clogged drain. and the temperature at the clog when the drain was opened, vary for the different examples; 5

however. in each example a composition comprising powdered aluminum. an alkali metal nitrate, and an al- Example I Ingredient Na P O Aluminum Powder (3) K (I Example 3 kali metal salt of an acid having at least one hydrogen atom with an ionization constant not exceeding 6.0 X 10 has been effective in opening a clogged drain.

The following examples are further illustrations of heat-producing drain-cleaner compositions of the present invention:

Example 4 Ingredient Ingredient Ethylencdiaminetutra- Ethylenediaminctctraacetic Acid t'lctraacetic Acid (Tetra- Sodium Salt) 36.0 Sodium Salt) 36.0 K NO Hut) K ND 59.0 Aluminum Powder t 3) 05 Aluminum Ponder [2) 0.5 K ct 47.5 K CI 4.5

lOlHlCi llillli'l'i Example 5 '2; Example 6 '4 ln rcdicnt Ingredient Nitrilotriacetic Acid Nitrilotriacetic Acid tI'ri-Sodium Salt) 311.0 ('l'ri-Sodium Salt) 311.0 K N0; tan Na NO 5 m Aluminum Ponder (3) 05 Aluminum Powder (3) 0.5 K (I 47.5 K Cl 45 IOtLll'Yr ltitLll' Example 7 Example 8 ln rcdicnt lnprcdicnt Nitrilotriacetic Acid N Hydroxyethylenetliamine- ('I'ri-Sodium Salt) 36.0 triacetic Acid (l'ri-Sodium "llll 36." Na N0 I61) K NO I61) Aluminum Powder 1 I) lh.7 Aluminum Powder (3) 0.5 Nit (I 3L3 K Cl 475 ")(Hl'l lOllll /i Example 9 Example l0 Ingredient Ingredient N-hydroxyethylenediamine- Diethylcnetriaminepenta ll'litLLlIL' Acid t'lri-Sodium acetic Acid tPenta-Sodium 'III) 36.0 Salt) 36.0 Na N0; 59.0 K NQ 16.0 Aluminum Powder (2) 0.5 Aluminum Powder (3) 0.5 Na CI 4.5 K CI 47.5

lOlLlV/i HHLU /i Example ll Example I2 In redicnt Ingredient Dieth lcnetriamincpenta- Saccltarin (Sodium acetic Acid tPentarSodium Salt) 360 Salt) 36.0 K hlt') 59.0 K NO 16.0 Aluminum Powder (2) 0.5 Aluminum Powder (3) 0.5 NaCl 4.5 K CI 47.5

llNHl /r HNHl'fi Example [3 Example I4 Ingredient Ingredient Saceharin (Sodium Sacchurin (Sodium Salt) 730 Salt] 3h." Nit NO; in." K No, 59]] Aluminum Powder (2) 05 Aluminum Powder l) 0.5 K CI I0.5 K CI 4.5

Example I5 Ci Example In Ingredient Ingredient Para Hydroxyhenzoic Acid Para Hydroxybenzoic Acid [Di-Sodium Salt) 36.0 (Di-Sodium Salt) 36.1) Nu No In." Na NO: 59." Aluminum Powder (3) 0.5 Aluminum Powder (2) 0.5 Na (I 47.5 K Cl .5

100.0% HIIHI'Z Continued Example I7 Example l8 Ingredient Ingredient Para Hydroxybenroie Acid Hydroquinone lSodium (DLSodium Salt] 360 Salt] K N0 Inn K NO Aluminum Powder I I I 16.7 Aluminum Ponder (3) K (I 31.3 K Cl IIIIHW Example I! Esaniple Ill Ingredient Ingredient Hydroquinone (Sodium Alpha Aminoaeelic Acid Salt] 36.0 (Sodium Salt) Na IND 59.0 K NO, Aluminum Powder III 0.5 Aluminum Powder (3) Na (I 4.5 K Cl llIOlF/l Example II Example 2'. Ingredient Ingredient Alpha Aminoacetie Acid Salicylic Acid lSodium Salt] 10.1) (Di-Sodium Salt] s No. 59.0 K No. Aluminum Powder l [I5 Aluminum Ponder (3| K (I 4.5 K Cl lllllll'i Esample Z3 Ingredient Salicylic Acid (Di-Sodium SaItI .mo K NU, S HI Aluminum Powder I I I ".5 K (I 4.5

A unique feature otthe compositions of the invention is the prevention ofthe precipitation of AIIOH )3 in any appreciable amount. It would not be expected that the reaction product Na HPO, would be a strong enough base to convert most of the insoluble AI(CH);, to the more soluble sodium aluminate.

The reaction rate may be slowed by controlling the particle size of the ingredients and the reaction rate may be readily varied by changing the bulk density, granulation and relative proportions of ingredients. The reaction rate may also be controlled by fusing the dry mixture and then granulating.

FIG. 1 shows the effect of particle size and temperature when 30 grams of the product are added to I00 ml. of water. The composition and particle size range for samples shown in FIG. 1 are as follows:

Composition IFused-Granulated Screened) Particle Size tmieronsl 3h ll Inn IIIlLlV/i IIIIIIW Ingredient Sample C (9%) Sample E (Ii Aluminum Powder 4.l 4 'lri-sodium Phosphate 25.0 IUranularI 25.0 (Powdered) Potassium Nitrate 35.0 35.!) Potassium Chloride 35 .9 35 .9

IIIOJI'Z IUILO'f/r Bulk Density [.05 .85

A similar plot of the effect of composition is given in FIG. 2. The composition of each sample for FIG. 2 is given below.

The results presented in FIGS. I, 2, and 3 show the effect of composition, particle size. and bulk density on the delayed action of the produce.

What is claimed is:

t. A heat-producing. drain-cleaning composition comprising (a) powdered aluminum having a particle size from l to 300 microns. in an amount from about 0.5 to about l6.7% by weight; (b) an alkali tnetal nitrate in an amount front about [6 to about 59% by weight; and (c) an alkali metal salt of an acid, wherein said acid has at least one hydrogen atom with an ionization constant in water not exceeding 6.0 X l(). in an amount from about 36 to about 73.2% by weight. wherein said acid is a member of the group consisting of:

salicylic acid alpha Aminoacetic acid hydroquinone para hydroxybenzoic acid saccharin carbonic acid pyrophosphoric acid ethylenediaminetctraacetic acid diethylenetriaminepentaacctic acid NHydroxyethylenediaminetriacetic acid nitrilotriacetic acid phosphoric acid 2. A heat-producing, drain-cleaning composition comprising (a) powdered aluminum having a particle size from I to 300 microns, in an amount from about 0.5 to about 16.7% by weight; (b) an alkali metal nitrate in an amount from about l6 to about 59% by weight; and (c) an alkali metal salt of an acid, wherein said acid has at least one hydrogen atom with an ionization constant in water not exceeding 6.0 X IO', wherein the amount of said aluminum and of said salt is such that upon contact of said composition with water, the initial amount of heat produced will provide l the heat loss due to dissipation from the system and (2) sufficient heat to raise the temperature of the surrounding water and suspended solids so that the autocatalytic effect of the temperature will provide an in' creased rate of reaction resulting in a hot boiling mixture; the amount of said salt being from about 36 to about 73.2% by weight. wherein said acid is a member of the group consisting of;

salicylic acid alpha aminoacetic acid hydroquinone para hydroxybenzoic acid saccharin carbonic acid pyrophosphoric acid ethylenediaminetetraacetic acid diethylenctriaminepentaacetic acid N-hydroxyethylenediaminctriacetic acid nitrilotriacctic acid phosphoric acid 3. A composition according to claim 1 wherein nitrate is sodium nitrate.

4. A composition according to claim 1 wherein said nitrate is potassium nitrate.

5. A composition according to claim 1 wherein the nitrate is sodium nitrate and the salt is tri-sodium phosphate.

6. A composition according to claim 1 wherein the nitrate is potassium nitrate and the salt is tri-potassium phosphate.

said

7. A composition according to claim I wherein the nitrate is sodium nitrate and the salt is tri-potassium phosphate.

8. A composition according to claim 1 wherein the salt is tetrasodium pyrophosphate.

9. A composition according to claim 1 wherein the salt is sodium tripolyphosphate.

10. A composition according to claim 1 which additionally comprises 0.02% of a surfactant, wherein the surfactant is a member of the group consisting of sulfonated mineral oil, a combination of mono and disphosphate esters of an ethoxylated linear alcohol. and an oxyethylated primary straight chain alcohol wherein the alcohol contains from 12 to 20 carbon atoms.

11. A composition according to claim 1 which comprises additionally 36% potassium chloride.

12. A composition according to claim I wherein the nitrate is potassium nitrate and the salt is tri-sodium phosphate.

13. A composition according to claim 12 wherein the ingredients are present in the following amounts:

Aluminum Powder 5." grams Potassium Nitrate 591) grants 'l'ri-sodium Phosphate 361) grams,

14. A composition according to claim 7 wherein the ingredients are present in the following amounts:

Aluminum Powder l.7 grams Sodium Nitrate Ill. grams 'lri-potassium Phosphate IX} grams 15. A composition according to claim 12 wherein the ingredients are present in the following amounts:

Aluminum Powder 1.2 grams Potassium Nitrate (1.8 grams 'l'ri-sodium Phosphate 3.0 grams.

16. A composition according to claim 1 wherein the nitrate is sodium nitrate and the salt is di-sodium carbonate.

17. A composition according to claim 16 wherein the ingredients are present in the following amounts:

Aluminum Powder Sodium Nitrate Di-sodium Carbonate LS grants llt) grams ltxS grams.

Aluminum Powder 3.8 grams Potassium Nitrate 30." grams Di-sodiuni Carbonate 41.2 grams.

20. A composition according to claim 1 wherein the nitrate is potassium nitrate and the salt is tetra-sodium pyrophosphatc.

21. A composition according to claim 20 wherein the ingredients are present in the following amounts:

Aluminum Powder 4.2 grams Potassium Nitratc .101) grams l'ctrivsndium Pyrophosphatc Still grams.

22. A composition according to claim I whcrcin thc nitratc is potassium nitratc and the salt is tctrapotassium pyrophosphatc.

23. A composition according to claim 22 whcrcin the ingredients arc prcscnt in the following amounts:

Aluminum Ponder 2.5 grams Potassium Nitratc 20.0 grams [elm-potassium Pyrophosphat: 27.5 grams.

l whc rein said 29. A composition according to claim I wherein said acid is carbonic acid.

30. A composition according to claim I whcrcin said acid is phosphoric acid.

3]. A composition according to claim 1 whcrcin said acid is pyrophosphoric acid.

32. A composition according to claim 1 whercin said acid is cthylcncdiaminetctraacctic acid.

33. A composition according to claim I whcrcin said acid is dictl'iylcnctriamincpcntaacetic acid.

34. A composition according to claim I wherein said acid is N-hydroxycthylcncdiaminctriacctic acid.

35. A composition according to claim 1 whcrcin said acid is nitrilotriacctic acidv 36. A composition according to claim 30 which additionally contains 2% of a non-aqueous, tacky, liquid surfactant.

37. A drain-clcaning, hcat-producing composition in accordancc with claim 1 whcrcin said aluminum powdcr has a particle size of from l5 to 50 microns.

38. A hcatproducing. drain-cleaning composition according to claim I. whcrcin thc ingrcdients arc prcscm in an amount such that the mole ratio of the aluminum powdcr to the salt of the acid to the alkali metal 

1. A HEAT-PRODUCING, DRAIN-CLEANING COMOSITION COMPRISING (A) POWDERED ALUMINUM HAVING A PARTICLE SIZE FROM 1 TO 300 MICRONS, IN AN AMOUNT FROM ABOUT 0.5 TO ABOUT 16.7% BY WEIGHT; (B) AN ALKALI METAL NITRATE IN AN AMOUNT FROM ABOUT 16 TO ABOUT 59% BY WEIGHT; AND (C) AN ALKALI METAL SALT OF AN ACID WHEREIN SAID ACID HAS AT LEAST ONE HYDROGEN ATOM WITH AN IONIZATION CONSTANT IN WATER NOT EXCEEDING 6.0X10**-9, IN AN AMOUNT FROM ABOUT 36 TO ABOUT 73.2% BY WEIGHT, WHEREIN SAID ACID IS A MEMBER OF THE GROUP CONSISTING OF: SALICYLIC ACID ALPHA AMONIACETIC ACID HYDROQUINONE PARA HYDROXYBENZOIC ACID SACCHARIN CARBONIC ACID PYROPBOSPHORIC ACID ETHYLENEDIAMINEYETRAACETIC ACID DIETHYLENETRIANMINEPENTAACETIC ACID N-HYDROXYETHYLENEDIAMINETRIACETIC ACID
 2. A heat-producing, drain-cleaning composition comprising (a) powdered aluminum having a particle size from 1 to 300 microns, in an amount from about 0.5 to about 16.7% by weight; (b) an alkali metal nitrate in an amount from about 16 to about 59% by weight; and (c) an alkali metal salt of an acid, wherein said acid has at least one hydrogen atom with an ionization constant in water not exceeding 6.0 X 10 9, wherein the amount of said aluminum and of said salt is such that upon contact of said composition with water, the initial amount of heat produced will provide (1) the heat loss due to dissipation from the system and (2) sufficient heat to raise the temperature of the surrounding water and suspended solids so that the auto-catalytic effect of the temperature will provide an increased rate of reaction resulting in a hot boiling mixture; the amount of said salt being from about 36 to about 73.2% by weight, wherein said acid is a member of the group consisting of; salicylic acid alpha aminoacetic acid hydroquinone para hydroxybenzoic acid saccharin carbonic acid pyrophosphoric acid ethylenediaminetetraacetic acid diethylenetriaminepentaacetic acid N-hydroxyethylenediaminetriacetic acid nitrilotriacetic acid phosphoric acid
 3. A composition according to Claim 1 wherein said nitrate is sodium nitrate.
 4. A composition according to claim 1 wherein said nitrate is potassium nitrate.
 5. A composition according to claim 1 wherein the nitrate is sodium nitrate and the salt is tri-sodium phosphate.
 6. A composition according to claim 1 wherein the nitrate is potassium nitrate and the salt is tri-potassium phosphate.
 7. A composition according to claim 1 wherein the nitrate is sodium nitrate and the salt is tri-potassium phosphate.
 8. A composition according to claim 1 wherein the salt is tetrasodium pyrophosphate.
 9. A composition according to claim 1 wherein the salt is sodium tripolyphosphate.
 10. A composition according to claim 1 which additionally comprises 0.02% of a surfactant, wherein the surfactant is a member of the group consisting of sulfonated mineral oil, a combination of mono and disphosphate esters of an ethoxylated linear alcohol, and an oxyethylated primary straight chain alcohol wherein the alcohol contains from 12 to 20 carbon atoms.
 11. A composition according to claim 1 which comprises additionally 36% potassium chloride.
 12. A composition according to claim 1 wherein the nitrate is potassium nitrate and the salt is tri-sodium phosphate.
 13. A composition according to claim 12 wherein the ingredients are present in the following amounts:
 14. A composition according to claim 7 wherein the ingredients are present in the following amounts:
 15. A composition according to claim 12 wherein the ingredients are present in the following amounts:
 16. A composition according to claim 1 wherein the nitrate is sodium nitrate and the salt is di-sodium carbonate.
 17. A composition according to claim 16 wherein the ingredients are present in the following amounts:
 18. A composition according to claim 1 wherein the nitrate is potassium nitrate and the salt is di-sodium carbonate.
 19. A composition according to claim 18 wherein the ingredients are present in the following amounts:
 20. A composition according to claim 1 wherein the nitrate is potassium nitrate and the salt is tetra-sodium pyrophosphate.
 21. A composition according to claim 20 wherein the ingredients are present in the following amounts:
 22. A composition according to claim 1 wherein the nitrate is potassium nitrate and the salt is tetra-potassium pyrophosphate.
 23. A composition according to claim 22 wherein the ingredients are present in the following amounts:
 24. A composition according to claim 1 wherein said acid is salicylic acid.
 25. A composition according to claim 1 wherein said acid is alpha aminoacetic acid.
 26. A composition according to claim 1 wherein said acid is hydroquinone.
 27. A composition according to claim 1 wherein said acid is parahydroxybenzoic acid.
 28. A composition according to claim 1 wherein said acid is saccharin.
 29. A composition according to claim 1 wherein said acid is carbonic acid.
 30. A composition according to claim 1 wherein said acid is phosphoric acid.
 31. A composition according to claim 1 wherein said acid is pyrophosphoric acid.
 32. A composition according to claim 1 wherein said acid is ethylenediaminetetraacetic acid.
 33. A composition according to claim 1 wherein said acid is diethylenetriaminepentaacetic acid.
 34. A composition according to claim 1 wherein said acid is N-hydroxyethylenediaminetriacetic acid.
 35. A composition according to claim 1 wherein said acid is nitrilotriacetic acid.
 36. A composition according to claim 30 which additionally contains 2% of a non-aqueous, tacky, liquid surfactant.
 37. A drain-cleaning, heat-producing composition in accordance with claim 1 wherein said aluminum powder has a particle size of from 15 to 50 microns.
 38. A heat-producing, drain-cleaning composition according to claim 1, wherein the ingredients are present in an amount such that the mole ratio of the aluminum powder to the salt of the acid to the alkali metal nitrate is 8 to 5 to
 3. 